Biofuel Feedstocks and Production

Lecture Six

Cellulose, Hemicellulose and Lignin

Biological and Ecological Engineering Department

Summary of Lecture Five

What are the main constituents of lignocellulosic feedstocks? Cellulose: Homopolymer of glucose consisting of (14 bonds. It differs from another polymer of glucose, starch that consists of (14) bonds Hemicellulose: Heteropolymer of pentoses (xylose and arabinose) and hexoses (glucose, galactose, mannose) and sugar acids (acetic). Hardwood hemicelluloses are xylans whereas softwood consists of glucomannans Lignin: A racemic, heteropolymer consisting of three hydroxycinnamyl alcohol monomers differing in their degree of methoxylation: p-coumaryl, coniferyl and sinapyl alcohols
Ref: http://bioenergy.ornl.gov/main.aspx and GMIS, Oak Ridge National Laboratory

Biofuel Feedstocks and Production

Cellulose Allomorphs
Cellulose: There are six polymorphs of cellulose. Cellulose I occurs naturally while the polymorphs are formed by physical treatments. Cellulose II is thermodynamically most stable form. Allomorphs are identified by X-ray or electron diffraction.
Regeneration

Cellulose I
NH3 (l) - NH3(g)

Mercerization

Cellulose II
NH3 (l) - NH3(g)

Cellulose IIII
Heat

Cellulose IIIII
Heat

Cellulose IV1
Ref: OSullivan (1997)

Cellulose IVII

Biofuel Feedstocks and Production

Cellulose Allomorphs

Biofuel Feedstocks and Production

Cellulose Allomorphs

Regeneration

Cellulose I
NH3 (l) - NH3(g)

Mercerization

Cellulose II

Cellulose IIII

Ref: French and Johnson (2007)

Biofuel Feedstocks and Production

Cellulose Hemicellulose

Cellulose xyloglucan network Biofuel Feedstocks and Production

Hemcellulose
Second most abundant biopolymer on earth. Hemicellulose: Heteropolymer of pentoses (xylose and arabinose) and hexoses (glucose, galactose, mannose) and sugar acids Hemicelluloses are made of xylan (xylose, arabinose and glucuronic acid) backbone Xylan backbone is highly substituted by side chains consisting of xylose, arabinose and galucuranic acids Heteroxylans are highly cross linked with diferulic bridges (with other xylans), isodityrosine bridges (structural proteins) Hemicellulose can be extracted by alkali or hot water and hydrolyzed by dil. H2SO4.

Ref: Saha (2003)

Biofuel Feedstocks and Production

Hemcellulose

Important Monomers of Hemicellulose 1. 2. 3. 4. 5. 6. 7. Xylose Glucose Mannose Galactose Arabinose Glucuronic acid Acetic acid

Ref: Hansen and Plackett (2008)

Biofuel Feedstocks and Production

Hemcellulose
Hemicellulose: Heteropolymer of pentoses (xylose and arabinose) and hexoses (glucose, galactose, mannose) and sugar acids

Hemicelluloses can be classified into four types based on main type of sugar residue:
Xylans : secondary cell walls of hardwood and herbaceous plants. Xyloglucans: primary cell walls of higher plants; bound to cellulose.

Mannans : Secondary cell walls of conifers (softwood) and Leguminosae.

Mixed linkage -glucans: Common in Poales (members of grass family) and pteridophytes (vascular plants that do not have flowers and seeds and reproduce by spores).

Ref: Schadel et al. (2009)

Biofuel Feedstocks and Production

Hemcellulose
Heteroxylan structure

Corn fiber cell structure

Ref: Saha (2003)

Biofuel Feedstocks and Production

Hemcellulose in plants
Heteroxylan structure

Ref: Schadel et al. (2009)

Biofuel Feedstocks and Production

Hemcellulose in plants
Heteroxylan structure

Ref: Schadel et al. (2009)

Biofuel Feedstocks and Production

Hemcellulose Composition Variation

Heteroxylan structure

Ref: Schadel et al. (2009)

Biofuel Feedstocks and Production

Lignin Composition and Synthesis

Ref: Eggeling (1983)

Biofuel Feedstocks and Production

Lignin Composition and Synthesis

Lignin: A racemic, heteropolymer consisting of three hydroxycinnamyl alcohol monomers (C9) differing in their degree of methoxylation: pcoumaryl, coniferyl and sinapyl alcohols

Ref: Boerjan at al. (2003) and Holladay et al (2007)

Biofuel Feedstocks and Production

Lignin Composition and Synthesis

There are other monomer units in minor concentrations

Ref: Boerjan at al. (2003)

Biofuel Feedstocks and Production

Lignin Composition and Synthesis

Composition of Lignin is dependent on the source of feedstocks Softwood lignins are rich in coniferyl alcohol (90%) Hardwood lignins are made of about equal amounts of coniferyl and synapyl alcohols Grasses consist of coniferyl and synaply alcohol and significant amounts of p-coumaryl alcohol (10-20%)

Ref: Boerjan at al. (2003)

Biofuel Feedstocks and Production

Lignin Composition and Synthesis

Composition of Lignin is dependent is also dependent on the method of extraction.

Kraft Lignin
Sulfite Lignin Organosolv Lignin Pyrolysis Lignin Steam explosion Lignin Dilute Acid Lignin Alkaline Oxidative Lignin

Ammonia fiber Explosion (AFEX)

Hot water
Ref: Boerjan at al. (2003)

Biofuel Feedstocks and Production

Cellulosic Ethanol

Ref: http://genomicsgtl.energy.gov/biofuels/.

Biofuel Feedstocks and Production

Thank you

Biofuel Feedstocks and Production